DE86223C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

α, 6., - naphthylenediamines.

In the first three addenda to Patent No. 78497 (Patent Specifications No. 79189, 80778 and 86222) it has been shown that when the substituted m-naphthylenediamines or theirs are heated Sulphonic acids with azo compounds - regardless of whether the latter contain basic groups or not - in the presence of a solvent or diluent (such as alcohol or glacial acetic acid) blue to bluish-red azine dyes of the rosindulin series are formed.

When using neutral or basic solvents or diluents and when Temperatures above ioo ° other dyes are formed, probably by this the amine split off the azo compound or the diluent in the reaction participates.

While z. B. by heating azobenzene with ditolyl-aj ß ₂ - naphthylenediamine - cc ₄ -sulphonic acid in glacial acetic acid solution and sulphires of the initially formed product a dye is obtained, which is changed to yellow by alkali, the alkali produced in phenol solution is and shows that the former have a much more bluish shade.

The new dyes that are created in this way belong same class of. Dyes on how. those in the main patents and the first three additions described.

Example I.

100 parts of di-p-tolyl-ctj ß ₂ -naphtylendiamina -sulfosäure _4, 66 parts of azobenzene and 2ooTheile phenol are heated in a kettle equipped with a stirrer for 5 hours to 130 ^0th The phenol is then removed by alkali and the sodium salt of rosindulin monosulfonic acid, which is sparingly soluble in water, is obtained in crystals. By treatment with sulphonating agents, the monosulphonic acid is easily converted into a disulphonic acid which can be leveled out well and which stains W ₁ oils in bluish-red, alkali-fast and acid-fast shades.

Example II.

₁ ß _2-a -naphtylendiamin ₄ -sulfosäure 10 parts Ditolyl- (X, 12 parts Benzolazodimethylanilinm-sulfonic acid and 80 parts of phenol are heated for several hours at 140 to 150 ^0th The blue melt is poured into water and tied with ammonia, the phenol. The dye separates out when it cools down.

The supernatant liquid is poured off ^ the residue dissolved in plenty of hot water, weakly acidified with hydrochloric acid and the Solution filtered at the boil. From the filtrate The dye crystallizes out in shiny flakes on cooling. He can as such or after it has been transformed into a salt in a known manner, can be used, equalizes very well and produces a lot on wool

clear blue tones that are not significantly different from those that come with the corresponding, in glacial acetic acid solution from the two components used according to the procedure of the first supplementary patent no. 79189 Dye can be obtained.

Example III.

50 kg diphenyl-cij ß. _2- naphthylenediamine-a ₄ -sulfonic acid are dissolved in 100 kg of phenol at water bath temperature and 80 kg of benzene- azophenyl -CL ₁ -naphthylamine-a ₄ -sulfonic acid are added. The mixture is heated for 4 to 5 hours at 140 to 150 ⁰ until the melt has assumed a green color. It is then poured into water to which 130 kg of sodium hydroxide solution (3 5 per cent.) Have been added. The precipitated dye is filtered and redissolved in water. It dissolves in hot water with a green-blue color and is resistant to alkalis and dilute acids. He dyes wool in clear, blue-green tones and these dyes show the property that they do not change their shade in lamplight.

Example IV.

Diphenyl-ttj ß ₂ -naphthylenediamine-a ₄ -sulfonic acid and p-ethoxyazobenzene are heated ^{to 130 to 140 0} with four times the amount of phenol in a ratio of 2: 3 molecules. The melt obtained is either poured into water and the phenol removed with caustic soda, or added directly to a lot of alcohol. The azin monosulfonic acid then crystallizes out. By sulphonation with 4 parts of cone. Sulfuric acid produces a polysulfonic acid that produces violet-blue tones on wool.

Instead of phenol, its homologues, aniline and its Use homologues etc. When using aniline, etc., the excess solution or. After the reaction has ended, the diluent is either distilled off with steam or possibly removed by boiling with dilute hydrochloric acid.

The azo compounds used in the examples can be replaced by any other azo, amidoazo, oxyazo derivatives and their substitution products. Instead of the diphenyl- or ditolyl-flj ß ₂ -naphthylenediamine sulfonic acids used, other derivatives of the substituted m-naphthylenediamine can also be used. In so far as the resulting products prove to be too sparingly soluble in water, they can be made easily soluble by treatment with sulphonating agents such as concentrated or fuming sulfuric acid, sulfuric acid chlorohydrin, sulfuric acid and phosphoric acid, etc.

The following are the coloring properties of some of the resulting dyes.

Dye from:

dyes wool:

Di-p-tolyl-ttj ß ₂ -naphthylenediamine-a ₄ -sulfonic acid and azobenzene in phenol solution. Subsequently sulfated

Diphenyl-aj ß ₂ -naphthylenediamine-a ₄ -sulfonic acid and azobenzene in aniline solution. Subsequently sulfated

Diphenyl-ctj ß ₂ -naphthylenediamine-ß ₃ -sulfonic acid and azobenzene in phenol solution. Subsequently sulfated

Di-p-tolyl-ttj ß ₂ -naphthylenediamine-a ₄ -sulfonic acid and amidoazobenzene in

Phenol solution. Subsequently sulfated

Di-p-tolyl-aj ß ₂ -naphthylenediamine-a ₄ -sulfonic acid and benzolazodimethyl-

aniline-m-sulfonic acid

Phenyl-p-tolyl-aj ß ₂ -naphthylenediamine-ß ₄ -sulfonic acid (from phenyl-a, -naphthylamine -ß ₂ ß ₄ -disulfonic acid and p-toluidine according to patent no. 78854)

and Benzolazo-aj-naphthylamine-β ^ sulfonic acid in phenol solution

Di-p-tolyl-ttj ß ₂ -naphtylamine-ß ₃ -sulfonic acid and benzene-azophenyl-a-naph-

tylamine in phenol solution. Subsequently sulfated

Diphenyl-ftj ß ₂ -naphthylenediamine-a ₄ -sulfonic acid and benzene-azophenyl-ctj-

naphthylamine-a ₄ -sulfonic acid in phenol solution

Ethyl-p-tolyl-ttj ß ₂ -naphthylamine-ß ₄ -sulfonic acid (from ethyl-aj-naphthylamine-ß ₂ ß ₄ -disulfonic acid and p-toluidine according to patent no. 78854) and

Benzolazotolyl-ctj-naphthylamine-c ^ -sulfonic acid in phenol solution

Diphenyl-ctj ß ₂ -naphthylenediamine-a ₄ -sulfonic acid and Aetlioxyazobenzol in

Phenol solution. Subsequently sulfated ....... .... . . ·. . ■: ''.

Di-p-tolyl-aj ß ₂ -naphthylenediamine-a ₄ -sulfonic acid and ethoxyazobenzene in phenol solution. Subsequently, V. sulfated ..... ^!

violet red

violet red

violet red

violet

blue

blail
blue

blue green

green Blue
violet blue
violet blue.

Claims (3)

Patent claims: ι. Innovation in the process of Patents No. 79189, 80778 and 86222 (additions to Patent No. 78497), consisting in the fact that the substituted Ct ₁ ß. ₂ -Naphthylenediamines or their sulfonic acids with azo bodies, amido or oxyazo bodies or their derivatives in the presence of a neutral or. basic solution or Diluent heated to temperatures above 100 °. 2. Conversion of the process obtainable according to the process protected by claim Dyes, insofar as they are basic, insoluble or sparingly soluble, in easily soluble dye polysulphonic acids by treatment with sulphurizing agents. 3. The execution of the process protected by the preceding patent claims using. a) the following Ci ₁ ß ₂ - naphthylenediamine derivatives: Diphenyl (or di-p-tolyl) Ci ₁ ß ₂ -naphthylenediamine -a ₄ -sulfonic acid, diphenyl- (or di-p-tolyl-) S ₁ ß ₂ -naphthylenediamine-ß ₃ -sulfonic acid, phenyl - ρ - tolyl - Ct ₁ ß ₂ -naphthylenediamine _{ß 4} -sulfonic acid, ethyl-p-tolyl-ttj ß ₂ -naphthylenediamine-ß ₄ -sulfonic acid; b) the following azo compounds: Azobenzene, amidoazobenzene, benzolazodimethylaniline - m - sulfonic acid, benzolazo-cij - naphthylamine-ß ₄ - sulfonic acid, benzolazophenyl - a - naphthylamine, benzolazophenyl (or tolyl) aj-naphthylamine-a ₄ -sulfo-benzoic acid, c) the following solution respectively. Diluent: Phenol, aniline.